US4025089A - Pressure-sensitive copying or recording material - Google Patents

Pressure-sensitive copying or recording material Download PDF

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Publication number
US4025089A
US4025089A US05/711,195 US71119576A US4025089A US 4025089 A US4025089 A US 4025089A US 71119576 A US71119576 A US 71119576A US 4025089 A US4025089 A US 4025089A
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US
United States
Prior art keywords
carbon atoms
alkyl
halogen
material according
formula
Prior art date
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Expired - Lifetime
Application number
US05/711,195
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English (en)
Inventor
Robert Garner
Jean-Claude Petitpierre
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Novartis Corp
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Ciba Geigy Corp
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Publication of US4025089A publication Critical patent/US4025089A/en
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/124—Duplicating or marking methods; Sheet materials for use therein using pressure to make a masked colour visible, e.g. to make a coloured support visible, to create an opaque or transparent pattern, or to form colour by uniting colour-forming components
    • B41M5/132—Chemical colour-forming components; Additives or binders therefor
    • B41M5/136—Organic colour formers, e.g. leuco dyes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/914—Transfer or decalcomania
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles

Definitions

  • the subject of the present invention is a pressure-sensitive copying or recording material which contains, in its colour-producing system, as the colour-forming agent, at least one azomethine compound of the formula ##STR2##
  • R 1 , R 2 , R 3 and R 4 each denote hydrogen, alkyl with 1 to 4 carbon atoms, cyanoalkyl with 2 to 5 carbon atoms, unsubstituted benzyl or phenyl, or benzyl or phenyl substituted by halogen, alkyl with 1 to 4 carbon atoms or alkoxy with 1 to 4 carbon atoms, or R 1 and R 2 conjointly denote alkylene with 4 or 5 carbon atoms and/or R 3 and R 4 conjointly denote alkylene with 4 or 5 carbon atoms,
  • X 1 and X 2 each denote hydrogen, halogen, alkyl with 1 to 4 carbon atoms or alkoxy with 1 to 4 carbon atoms
  • A denotes naphthylene or
  • R 1 , R 2 , R 3 and R 4 each denote hydrogen, alkyl with 1 to 4 carbon atoms, cyanoalkyl with 2 to 5 carbon atoms, benzyl or phenyl, or R 1 and R 2 conjointly denote alkylene with 4 or 5 carbon atoms and/or R 3 and R 4 conjointly denote alkylene with 4 or 5 carbon atoms
  • X 1 and X 2 each denote hydrogen, halogen, alkyl with 1 to 4 carbon atoms or alkoxy with 1 to 4 carbon atoms
  • A denotes naphthylene or phenylene, which is optionally further substituted by halogen, alkyl with 1 to 4 carbon atoms or alkoxy with 1 to 4 carbon atoms
  • n denotes 1 or 2.
  • radicals R 1 and R 3 , the radicals R 2 and R 4 and X 1 and X 2 preferably have the same meaning.
  • Preferred colour-forming agents correspond to the formula ##STR3## wherein R 5 and R 6 each denote alkyl with 1 to 4 carbon atoms, benzyl or phenyl or R 5 and R 6 conjointly denote alkylene with 4 or 5 carbon atoms, X 3 denotes hydrogen, alkyl with 1 to 4 carbon atoms or alkoxy with 1 to 4 carbon atoms, A 1 denotes phenylene, which can be further substituted by halogen, alkyl with 1 to 5 carbon atoms, alkoxy with 1 to 4 carbon atoms, phenoxy, chlorophenoxy, benzoylamino or alkanoylamino with 2 to 4 carbon atoms, and n denotes 1 or 2.
  • azomethine compounds which are of particular industrial importance, and thus are particularly preferred, can be represented by the following formula (3) ##STR4## wherein R 7 and R 8 each denote alkyl with 1 to 4 carbon atoms or benzyl, X 4 denotes hydrogen, halogen, preferably chlorine, or methyl, methoxy or ethoxy, Y 1 denotes hydrogen, halogen, methyl, methoxy, phenoxy, chlorophenoxy, benzoylamino or alkanoylamino with 2 to 4 carbon atoms and Y 2 denotes hydrogen, halogen, methoxy or alkyl with 1 to 5 carbon atoms.
  • colour-forming agents correspond to the formula ##STR6## wherein R 7 and R 8 each denote alkyl with 1 to 4 carbon atoms or benzyl, Y 3 denotes hydrogen, alkyl with 1 to 4 carbon atoms or methoxy and Y 4 denotes hydrogen, methyl or methoxy.
  • R radicals in the formulae (1) to (5) can differ from one another or, preferably, can be identical.
  • R radicals or X radicals denote alkyl
  • alkyl represents, for example, n-butyl, iso-butyl, tert.-butyl, sec.-butyl, n-propyl, isopropyl or, above all, ethyl or, preferably, methyl.
  • cyanoalkyl can, for example, denote 4-cyanobutyl, 3-cyanopropyl or, above all, 2-cyanoethyl.
  • Preferred substituents in the benzyl or phenyl group of the R radicals are, for example, halogens, methyl or methoxy.
  • Examples of such araliphatic and aromatic radicals are o- or p-methylbenzyl, o- or p-chlorobenzyl, o- or p-tolyl, xylyl, o-, m- or p-chlorophenyl and o- or p-methoxyphenyl.
  • the R radicals conjointly are alkylene, they then form, conjointly with the nitrogen atom to which they are bonded, a heterocyclic ring, such as, for example, a piperidine, pipecoline or pyrrolidine ring.
  • the alkoxy radicals are represented by the alkoxy radicals which correspond to the alkyl radicals, such as, for example, methoxy, ethoxy, isopropoxy or tert.-butoxy.
  • the phenylene radical A can advantageously also contain an acylamino group of 1 to 9 carbon atoms, especially when n is 1.
  • acylamino groups which may be mentioned in particular are benzoylamino or alkanoylamino of 2 to 4 carbon atoms, such as acetylamino or propionylamino.
  • halogen is, for example, iodine, fluorine, bromine or, preferably, chlorine.
  • the present colour-forming agents are in themselves known or are manufactured by known and conventional methods.
  • they can be manufactured by subjecting at least one aldehyde of the formula ##STR7## wherein R 1 , R 2 , R 3 , R 4 , X 1 and X 2 have the indicated meaning, to a condensation reaction with an amine of the formula wherein A and n have the indicated meaning, at elevated temperature, either in the absence of a solvent or, preferably, in an organic solvent, such as in a lower alcohol, for example ethanol.
  • the reaction is preferably carried out in the presence of a catalyst, for example acetic acid or a tertiary amine.
  • the reaction product of the formula (1) can be further purified by recrystallising it from methanol, ethanol or similar solvents.
  • the colour-forming agents of the formulae (1) to (5) are usually colourless or at most slightly coloured. When these colour-forming agents are brought into contact with an acid developer, that is to say an electron acceptor, they give intense yellow to orange colour shades which have excellent fastness to light.
  • Typical examples of electron acceptors are attapulgus clay, Silton clay, silicon dioxide, bentonite, halloysite, aluminium oxide, aluminium sulphate, aluminium phosphate, zinc chloride, kaolin or any desired acid clay or organic compounds which have an acid reaction, such as, for example, phenols, which are optionally substituted in the ring, salicylic acid or salicylic acid esters and their metal salts and also a polymeric material which has an acid reaction such as, for example, a phenolic polymer, an alkylphenol/acetylene resin, a maleic acid/rosin resin or a partially or completely hydrolysed polymer of maleic anhydride and styrene, ethylene, vinyl methyl ether or carboxypolymethylene.
  • Preferred coreactants are attapulgus clay, Silton clay or a phenol-formaldehyde resin. These electron acceptors are preferably applied in the form of a layer to the front of the receiving sheet.
  • the colour-forming agents used according to the invention display an improved fastness to light and colour intensity.
  • a pressure-sensitive copying or recording material comprises, for example, at least one pair of sheets, which contain at least one colour-forming agent of the formula (1), dissolved in an organic solvent and optionally in micro-capsules which can be broken open by pressure, and a solid electron acceptor. When it comes into contact with the electron acceptor substance, the colour-forming agent gives a coloured mark at the points at which pressure has been applied.
  • these colour-forming agents are enclosed in micro-capsules.
  • the capsules are broken open by pressure, for example by means of a pencil, and if the solution of the colour-forming agent is transferred, in this way, to an adjacent sheet which is coated with a substrate which can act as an electron acceptor, a coloured image is produced.
  • This new colour results from the dyestuff which has thus been formed and which absorbs in the visible region of the electromagnetic spectrum.
  • the colour-forming agents are preferably encapsulated in the form of solutions in organic solvents.
  • suitable solvents are non-volatile solvents, for example a polyhalogenated diphenyl, such as trichlorodiphenyl, and a mixture thereof with liquid paraffin, tricresyl phosphate, di-n-butyl phthalate, dioctyl phthalate, trichlorobenzene, nitrobenzene, trichloroethyl phosphate, petroleum ether, hydrocarbon oils, such as paraffin, alkylated derivatives of diphenyl, naphthalene or triphenyl, terphenyl, partially hydrogenated terphenyl or other chlorinated or hydrogenated, condensed, aromatic hydrocarbons.
  • suitable solvents are non-volatile solvents, for example a polyhalogenated diphenyl, such as trichlorodiphenyl, and a mixture thereof with liquid paraffin, tricresyl
  • the walls of the capsules are preferably formed uniformly, by coacervation forces, around the droplets of the solution of the colour-forming agent, the encapsulating material consisting of gelatine, such as is described, for example, in U.S. Pat. No. 2,800,457.
  • the capsules can preferably be formed from an aminoplast or modified aminoplasts by polycondensation, as described in British Patent Specifications 989,264, 1,156,725, 1,301,052, 1,355,124 or 1,389,238.
  • micro-capsules containing the colour-forming agents of the formula (1) can be used for the manufacture of pressure-sensitive copying materials of very diverse known types.
  • the various systems essentially differ from one another in the location of the capsules and of the colour reagents and in the carrier material.
  • a preferred arrangement is that in which the encapsulated colour-forming agent is applied, in the form of a layer, to the rear of a transfer sheet and the electron acceptor substance is applied, in the form of a layer, to the front of a receiving sheet.
  • the microcapsules containing the colour-forming agent, and the developer are in or on the same sheet, in the form of one or several separate layers, or in the paper pulp.
  • Such pressure-sensitive copying materials are described, for example, in U.S. Pat. Nos. 2,730,457, 2,932,582, 3,418,250, 3,418,656, 3,427,180 and 3,516,846. Further systems are described in British Patent Specifications 1,042,596, 1,042,597, 1,042,598, 1,042,599, 1,053,935 and 1,517,650. Micro-capsules which contain the colour-forming agents of the formula (1) are suitable for each of these systems and for other pressure-sensitive systems.
  • the capsules are preferably fixed to the carrier by means of a suitable adhesive.
  • a suitable adhesive are, in the main, paper coating agents, such as gum arabic, polyvinyl alcohol, hydroxymethylcellulose, casein, methylcellulose or dextrin.
  • paper which is used here comprises not only normal papers of cellulose fibres but also papers in which the cellulose fibres have been replaced (partially or completely) by fibres of synthetic polymers.
  • the following colour-forming agents 2.4 g of a mixture of the 3-(2'-ethoxy-4'-diethylaminophenyl)-2-(1"-ethyl-2"-methylindol-3"-yl)-5- and -6-nitrophthalide isomers, 0.54 g of 3,3-bis-(1'-n-octyl-2'-methylindol-3'-yl) phthalide and 0.06 g of the colour-forming agent No. 1 in Table 1, are dissolved in 97 g of partially hydrogenated terphenyl.
  • a paper is also coated with the capsule mass, in the same way as indicated in Example 1.
  • this paper is brought into contact with a paper coated with Silton Clay, a stable, deep blue image is obtained.
  • Example 2 The same colour-forming agents as those indicated in Example 2 are dissolved and encapsulated. A paper is then coated with the capsule mass. The weight ratio is, however, 3:0.2:0.05 instead of 2.4:0.54:0.6.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Color Printing (AREA)
US05/711,195 1975-08-12 1976-08-03 Pressure-sensitive copying or recording material Expired - Lifetime US4025089A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH1046675A CH593146A5 (en, 2012) 1975-08-12 1975-08-12
CH10466/75 1975-08-12

Publications (1)

Publication Number Publication Date
US4025089A true US4025089A (en) 1977-05-24

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ID=4363536

Family Applications (1)

Application Number Title Priority Date Filing Date
US05/711,195 Expired - Lifetime US4025089A (en) 1975-08-12 1976-08-03 Pressure-sensitive copying or recording material

Country Status (9)

Country Link
US (1) US4025089A (en, 2012)
JP (1) JPS5223406A (en, 2012)
AT (1) AT349495B (en, 2012)
BE (1) BE845063A (en, 2012)
CH (1) CH593146A5 (en, 2012)
DE (1) DE2635594A1 (en, 2012)
ES (1) ES450610A1 (en, 2012)
FR (1) FR2320833A1 (en, 2012)
GB (1) GB1510259A (en, 2012)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4521793A (en) * 1982-02-27 1985-06-04 Asahi Kasei Kogyo Kabushiki Kaisha Coloring method and color-forming material
US4888322A (en) * 1987-07-08 1989-12-19 Fuji Photo Film Co., Ltd. Recording material containing leuco dye
US4909954A (en) * 1986-02-03 1990-03-20 Minnesota Mining And Manufacturing Company Second harmonic generation with schiff bases
US5109107A (en) * 1990-12-21 1992-04-28 Hoecht Celanese Corp. Polyamide-imide polymers having fluorine-containing linking groups

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4189171A (en) * 1977-03-01 1980-02-19 Sterling Drug Inc. Marking systems containing 3-aryl-3-heterylphthalides and 3,3-bis(heteryl)phthalides

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3066023A (en) * 1958-12-19 1962-11-27 Azoplate Corp Member for electrophotographic reproduction and process therefor
US3697595A (en) * 1970-03-31 1972-10-10 Ibm Conjugated nitro amines
US3705184A (en) * 1972-01-17 1972-12-05 Polaroid Corp 1:1 chrome-complexed azomethine dye developers

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3066023A (en) * 1958-12-19 1962-11-27 Azoplate Corp Member for electrophotographic reproduction and process therefor
US3697595A (en) * 1970-03-31 1972-10-10 Ibm Conjugated nitro amines
US3705184A (en) * 1972-01-17 1972-12-05 Polaroid Corp 1:1 chrome-complexed azomethine dye developers

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4521793A (en) * 1982-02-27 1985-06-04 Asahi Kasei Kogyo Kabushiki Kaisha Coloring method and color-forming material
US4909954A (en) * 1986-02-03 1990-03-20 Minnesota Mining And Manufacturing Company Second harmonic generation with schiff bases
US4888322A (en) * 1987-07-08 1989-12-19 Fuji Photo Film Co., Ltd. Recording material containing leuco dye
US5109107A (en) * 1990-12-21 1992-04-28 Hoecht Celanese Corp. Polyamide-imide polymers having fluorine-containing linking groups

Also Published As

Publication number Publication date
ES450610A1 (es) 1977-08-01
FR2320833B1 (en, 2012) 1978-05-05
GB1510259A (en) 1978-05-10
JPS5223406A (en) 1977-02-22
AT349495B (de) 1979-04-10
BE845063A (fr) 1977-02-11
CH593146A5 (en, 2012) 1977-11-30
FR2320833A1 (fr) 1977-03-11
ATA596376A (de) 1978-09-15
DE2635594A1 (de) 1977-02-24

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